全 文 ：上的硫醇基结合, 抑制琥珀酰脱氢酶的活性, 从而严
重影响细胞的能量代谢, 最终导致细胞死亡; 32硝基
丙酸在人体引起的中毒症状表现为呕吐、共济失调、
抽搐、惊厥、昏迷等。文献报道的木蓝山豆根的中毒
症状与上述症状极为相似, 因此我们认为, 木蓝山豆
根中所含有的大量的 32硝基丙酸、co ronarian 和
co ro llin 很可能是引起毒性反应的主要成分。
References:
[ 1 ]　X iao P G1 R ecord of M od ern Ch ineseM eteria M ed ica (新编中
药志) [M ]1 Beijing: Chem ical Industry P ress, 20021
[ 2 ]　Xu G J , Xu L S1 A rrang em en t and Q ua lity S tudy of Com 2
m only U sed T rad itiona l Ch inese D rug s (常用中药材品种整理
和质量研究) [M ]1 Fuzhou: Fu jian Science and T echno logy
P ress, 19941
[ 3 ]　T hangaduraiD , Ram esh N , V isw anathan M B, et a l1 A no2
vel xan thene from Ind ig of era long eracem osa stem [J ]1 F i2
toterap ia , 2001, 72 (1) : 922941
[ 4 ]　H asan A , A hm ad I, Khan M A , et a l1 Two flavono l trig ly2
co sides from flow ers of Ind ig of era hebep eta la [J ]1 P hy to2 chem istry , 1996, 43 (5) : 1115211181[ 5 ]　Dom inguez X A , M artinez C, Calero A , et a l1 M exicanm edicinal p lan ts XXX I chem ical componen ts from“jiquelite”Ind ig of era suf f ru ticosa [J ]1 P lan ta M ed , 34 (1) : 17221751[ 6 ]　M ajak W , Benn M 1 A dditional esters of 32n itrop ropano icacid and gluco se from fru it of the N ew Zealand karaka tree,Cory nocarp us laev ig a tus [J ]1 P hy tochem istry , 1994, 35 (4) :90129031[ 7 ]　M ahato S B, Kundu A P1 13C2NM R spectra of pen tacyclictriterpeno ids——a comp ilation and som e salien t featu res [J ]1P hy tochem istry , 1994, 37 (6) : 1517215751[ 8 ]　Yu D Q , Yang J S1 H and book of A na ly tica l Chem istry A na l2y sis of N M R S p ectra (分析化学手册 第 7 分册 核磁共振波谱分析) [M ]1 V o lum e 7. 2nd ed1 Beijing: Chem ical Indus2try P ress, 19991[ 9 ]　H anley A B, M cbride J , O eh lsch lager S, et a l1 U se of a flowcell b io reacto r as a ch ron ic tox icity model system [J ]1 T ox i2col in V itro , 1999, 13: 84728511[ 10 ]　Peraica M , Radic′B, L ucic′A , et a l1 Toxic effects of m yto2tox ins in hum ans [J ]1 B u ll W orld H ea lth O rg an, 1999, 77(9) : 75427661
D iterpeno ids from E up horbia wa llich ii
W AN G H uan1, 2, ZHAN G X iao2feng2, M A Yun2bao 1, CA I X iang2hai1, W U D a2gang1, LUO X iao2dong13
(11 State Key L abo rato ry of Phytochem istry and P lan t R esources in W est Ch ina, Kunm ing Institu te of Bo tany,
Ch inese A cadem y of Sciences, Kunm ing 650204, Ch ina; 21 N o rthw est Inst itu te of P lateau B io logy,
Ch inese A cadem y of Sciences, X in ing 810001, Ch ina)
Abstract: Object　To study the chem ical con st ituen ts of E up horbia w a llich ii1 M ethods　T he con s2
t ituen ts w ere repeated ly separa ted and pu rif ied on silica gel co lum n1 T hey w ere iden t if ied on the basis of
spectra l m ethods1 Results　N ine diterpeno ids w ere ob ta ined from the roo ts of E 1 w a llich ii1 Among them
jo lk ino l B (É ) is la thyrane type; caudicifo lin (Ê ) , helio scop ino lides A (Ë ) , C (Ì ) , and E (Í ) belong
to ab ietane type; w h ile en t2at isane23Β, 16Α, 172t rio l (Î ) , en t216Α, 172dihydroxyat isan232one (Ï ) , en t2
3Β, (13S ) 2dihydroxyat is2162en2142one (Ð ) , and en t222hydroxy2at is21, 16 (17) 2dien23, 142dione (Ñ )
po ssess an en t2at isane skeleton1 Conclusion　A ll of them are iso la ted from E 1 w a llich ii fo r the first t im e1
Key words: E up horbia w a llich ii Hook. f. ; E up horbia L 1; la thyrane; ab ietane; en t2at isane
大果大戟的二萜成分
王　环1, 2, 张晓峰2, 马云保1, 蔡祥海1, 吴大刚1, 罗晓东1Ξ
(11 中国科学院昆明植物研究所 植物化学与西部植物资源持续利用国家重点实验室, 云南 昆明　650204;
21 中国科学院西北高原生物研究所, 青海 西宁　810001)
摘　要: 目的　研究大果大戟 E up horbia w allich ii 的化学成分。方法　采用反复硅胶柱色谱分离纯化, 通过波
谱方法鉴定化合物结构。结果　从大果大戟根部的乙醇提取物中分离得到 9 个二萜化合物, 其中 jo lk ino l B (É ) 是
千金二萜烷型; caudicifo lin (Ê ) , helio scop ino lides A (Ë ) , C (Ì ) 和 E (Í ) 是松香烷型; en t2atisane23Β, 16Α, 172
·116·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 6 期 2004 年 6 月
Ξ 收稿日期: 2003210212
基金项目: 中国科学院昆明植物研究所、植物化学与西部植物资源持续利用国家重点实验室基金资助3 通讯作者
t rio l (Î ) , en t216Α, 172dihydroxyatisan232one (Ï ) , en t23Β, (13S ) 2dihydroxyatis2162en2142one (Ð ) 和 en t222hydrox2
yatis21, 16 (17) 2dien23, 142dione (Ñ )属于对映2阿替斯烷型。结论　这些成分均为首次从该植物中分离得到。
关键词: 大果大戟; 大戟属; 千金二萜烷型; 松香烷型; 对映2阿替斯烷型
中图分类号: R 28411　　　文献标识码: A 　　　文章编号: 0253 2670 (2004) 06 0611 04
　　T he E up horbia L 1 is the largest genu s in the
spu rge fam ily, comp rising abou t 2 000 species1
M o re than 80% of them are dist ribu ted in Ch ina [1 ]1
V ariou s group s have been w o rked on the chem ical
con st ituen ts from the p lan ts of th is genu s[3～ 9 ] , and
m any b io logica l act ive diterpenes have been found1
E 1 w a llich ii Hook. f. , a t rad it ional m edicinal
p lan t, d ist ribu ted m ain ly in Q inghai P rovince, the
T ibet A u tonomou s R egion, and Yunnan P rovince
of Ch ina, has been u sed by T ibetan to cu re fu run2
cle, exan them a, and cu taneou s an th rax [2 ] 1 Its
chem ical con st ituen ts have no t p reviou sly been in2
vest iga ted1 F rom the alcoho l ex tract of the roo ts of
th is p lan t, one la thyrane type ( É [3 ] ) , fou r ab i2
etane type (Ê [5 ] - Í [6 ] ) , as w ell as fou r en t2at i2
sane type diterpenes (Î [7 ] , Ï , Ð [8 ] , Ñ [9 ] ) w ere
ob ta ined1 In th is paper the iso la t ion and structu re
elucidat ion of these compounds are repo rted1
1　Appara tus and plan t ma ter ia ls
M S spectra w ere ob ta ined w ith a V G A u to
Spec- 3000 spectrom eter, a t 70 eV fo r E I1 NM R
spectra w ere reco rded from a B ruker AM - 400
spectrom eter w ith TM S as in ternal standard1 A nd
Si gel (200- 300 m eshes) fo r co lum n ch rom atogra2
phy w as ob ta ined from the Q ingdao M arine Chem i2
cal Indu stry Facto ry1 E 1 w a llich ii w as co llected
from X inghai Coun ty, Q inghai P rovince of Ch ina,
in Ju ly 20011 It w as iden t if ied by P rof1 ZHAN G
X iao2feng1
2　Extraction and isola tion
A ir2dried roo t ( 10 kg ) w as ex tracted w ith
E tOH (95% ) fo r fou r t im es1 A fter removal of the
so lven t by evapo ra t ion, the residues w ere su spend2
ed in H 2O and ex tracted w ith CHC l3 fo r th ree
t im es1 T he CHC l3 fract ion w as concen tra ted in vac2
uo to g ive 100 g of the residue1 T he residue w as
separa ted repeated ly by ch rom atography on silica
gel co lum n and R P218 to affo rd É (50 m g) , Ê
( 10 m g) , Ë (60 m g) , Ì (20 m g) , Í (30 m g) ,Î (180 m g) , Ï (300 m g) , Ð (10 m g) , Ñ (55
m g) 1 T heir st ructu res are show n in F ig. 11
F ig11　Structures of d iterpeno ids É - Ñ
3　 Iden tif ica tion
Jo lk ino l B ( É ) : C 29H 36O 5, co lo rless o il;
1H 2NM R (CDC l3) : ∆ 3146 (1H , dd, 7, 1312 H z,
H 21Α) , 3161 (1H , d, 916 H z, H 25) , 4109 (1H , b r
s, H 23) , 6138 ( 1H , d, 1610 H z, H 22′) , 6194
( 1H , d, 1110 H z, H 212) , 712 - 714 ( 5H , m ) ,
7159 (1H , d, 1610 H z, H 23′) ; 13C2NM R (CDC l3) :∆ 4419 (C21) , 2916 (C22) , 7812 (C23) , 5211 (C2
4) , 5814 (C25) , 6411 (C26) , 3816 (C27) , 2312
(C28) , 3317 (C29) , 2612 (C210) , 3815 (C211) ,
14412 (C212) , 13318 (C213) , 19511 (C214) , 9119
(C215) , 1312 (C216) , 1919 (C217) , 2819 (C218) ,
1611 (C219) , 1213 (C220) , 16515 (C21′) , 11714
(C22′) , 14613 (C23′) , 13319 (C24′) , 12810 (C2
5′) , 12818 (C26′) , 13015 (C27′) , 12818 (C28′) ,
12810 (C29′) ; E I2M S m öz : 464 [M ]+ ( 3) , 333
(13) , 316 (3) , 131 (100) , 121 (18) , 103 (75) , 93
(27) , 77 (40) 1
Caudicifo lin ( Ê ) : C 20H 26O 4, co lo rless nee2
dles; 1H 2NM R (CDC l3) : ∆0171, 0183, 0192 (each
·216· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 6 期 2004 年 6 月
3H , s, M e×3) , 2163 (1H , d, 515 H z, H 29) , 4100
(1H , b r s, H 214) , 4162 (2H , b r s, H 217) , 5155
(1H , d, 515 H z, H 211) ; 13C2NM R (CDC l3 ) see
T ab le 1; E I2M S m öz : 330 [M ]+ (9) , 312 (19) ,
230 ( 23) , 188 ( 33) , 175 ( 84) , 162 ( 43) , 147
(18) , 137 (51) , 123 (37) , 109 (36) , 95 (84) , 81
(86) , 69 (100) , 55 (68) 1
H elio scop ino lide A (Ë ) : C20H 28O 3, co lo rless
needles; 1H 2NM R (CDC l3 ) : ∆ 0180, 0192, 1101
(each 3H , s, M e×3) , 1181 (3H , d, 114 H z, H 2
17 ) , 3126 ( 1H , dd, 414, 1118 H z, H 23) , 4184
( 1H , dd, 613, 1216 H z, H 212) , 6125 (1H , b r s,
H 214) ; 13C2NM R (CDC l3) is seen in T ab le 11
H elio scop ino lide C (Ì ) : C20H 26O 4, co lo rless
needles; 1H 2NM R (CDC l3 ) : ∆ 0168, 0191, 1123
(each 3H , s, M e×3) , 1184 (3H , d, 114 H z, H 2
17) , 3195 (1H , b r s, H 23) , 4184 (1H , dd, 613,
1216 H z, H 212 ) , 6132 ( 1H , b r s, H 214 ) ;
13C2NM R (CDC l3) is seen in T ab le 11
Table 1　13C-NM R spectra l data for compoundsÊ - Ñ (10 M Hz)
C Ê Ë Ì Í Î Ï Ð Ñ
　1 　4013 t　3714 t　5112 t　3713 t　3810 t　3719 t　3613 t　12419 d
2 1818 t 2715 t 20914 s 3413 t 2719 t 3410 t 2618 g 14411 s
3 4119 t 7815 d 8214 d 21515 s 7812 d 21715 s 7818 d 20017 s
4 3319 s 3910 s 4510 s 4715 s 3912 s 4716 s 3816 s 4318 s
5 5410 d 5413 d 5314 d 5416 d 5517 d 5516 d 5415 d 5312 d
6 2112 t 2314 t 2310 t 2415 t 1819 t 1916 t 1818 t 1911 t
7 3413 t 3618 t 3613 t 3615 t 4011 t 3817 t 3017 t 3110 t
8 6117 s 15114 s 14914 s 15012 s 3717 s 3218 s 4714 s 4810 s
9 5212 d 5115 d 5113 d 5015 d 5211 d 5018 d 5119 d 4818 d
10 4119 s 4112 s 4619 s 4018 s 3310 s 3712 s 3718 s 3911 s
11 10619 d 2715 t 2716 t 2717 t 2316 t 2312 t 2512 t 2810 t
12 14718 s 7519 d 7513 d 7516 d 3218 d 3211 d 4418 d 3810 d
13 14710 s 15610 s 15510 s 15515 s 2318 t 2314 t 7510 d 4415 t
14 5418 d 11412 d 11512 d 11416 d 2717 t 2714 t 21814 s 21614 s
15 12718 s 11614 s 11715 s 11619 s 5315 t 5214 t 4318 t 4215 t
16 16916 s 17513 s 17419 s 17510 s 7317 s 7412 s 14217 s 14615 s
17 5618 t 812 q 813 q 813 q 6913 t 6819 t 11017 t 10716 t
18 3319 q 2816 q 2915 q 2614 q 2816 q 2611 q 2814 q 2619 q
19 2213 q 1516 q 1614 q 2117 q 1613 q 2116 q 1516 q 2119 q
20 1515 q 1617 q 1713 q 1612 q 1412 q 1314 q 1410 q 1712 q
　　Compound Î w as m easured in C5D 5N , w h ile o ther compounds in CDC l3
w ith TM S as in ternal standard
H elio scop ino lide E (Í ) : C20H 26O 3, co lo rless
needles; 1H 2NM R (CDC l3) : ∆ 1102, 1104, 1109,
1180 (each 3H , s, M e×3) , 4184 (1H , m , H 212) ,
6130 (1H , s, H 214) ; 13C2NM R (CDC l3) is seen in
T ab le 1; E I2M S m öz : 314 [M ]+ (80) , 296 (45) ,
204 (30) , 177 (56) , 164 (100) , 151 (20) , 138
(60) , 123 (97) , 109 (19) , 96 (20) , 81 (14) , 69
(8) , 55 (14) 1
en t2A tisane23Β, 16Α, 172t rio l (Î ) : C 20H 34O 3,
w h ite pow ders; 1H 2NM R (C6D 5N ) : ∆ 0198, 1103,
1120 (each 3H , s, M e×3) , 3142 (1H , dd, 418,
1113 H z, H 23) , 3181, 3190 (2H , A bq, 1018 H z,
H 217) ; 13C2NM R (C 6D 5N ) is seen in T ab le 1; E I2
M S m öz : 322 [M ]+ (< 1) , 291 (100) , 273 (79) ,
255 (20) , 229 (15) , 135 (30) , 57 (24) 1
en t216Α, 172D ihydroxyat isan232one ( Ï ) :
C 20H 32O 3, co lo rless needles; 1H 2NM R (CDC l3 ) : ∆
2131 ( 1H , m , H 22Α) , 2156 ( 1H , m , H 22Β) ,
3140, 3153 (2H , A bq, 1018 H z, H 217) ; 13C2NM R
(CDC l3 ) is seen in T ab le 1; E I2M S m öz : 320
[M ]+ (< 1) , 289 (52) , 271 (17) , 247 (25) , 107
(37) , 95 (45) , 81 (47) , 69 (52) , 55 (100) 1
en t23Β, ( 13S ) 2D ihydroxyat is2162en2142one
( Ð ) : C 20H 30O 3, w h ite pow ders; 1H 2NM R
(CDC l3 ) : ∆ 3118 ( 1H , dd, 413, 1116 H z, H 23) ,
3182 (1H , d, 310 H z, H 213) , 4181 (1H , d, 110
H z, H 217 ) , 4197 ( 1H , b r s, H 217 ) ; 13C2NM R
(CDC l3 ) is seen in T ab le 1; E I2M S m öz : 318
[M ]+ (53) , 300 ( 9) , 243 ( 22) , 136 ( 80) , 121
(65) , 107 (66) , 97 (30) , 91 (70) , 81 (61) , 69
(70) , 57 (100) 1
en t222H ydroxy2at is21, 16 ( 17 ) 2dien23, 142
dione ( Ñ ) : C 20H 30O 3, w h ite pow ders; 1H 2NM R
(CDC l3 ) : ∆ 2175 ( 1H , t, 219 H z, H 212) , 4166
( 1H , b r s, H 217b ) , 4189 ( 1H , b r s, H 217a ) ,
6101 (1H , s, OH ) , 6106 (1H , s, H 21) ; 13C2NM R
(CDC l3 ) is seen in T ab le 1; E I2M S m öz : 314
[M ]+ (100) , 300 (32) , 243 (5) , 187 (25) , 154
(14) , 55 (7) 1
References:
[ 1 ]　Sh i Y P, J ia Z J1 Recen t studies on diterpene esters and their
b ioactivit ies from E up horbia genus in Ch ina [J ]1 Chem J
Ch in U n iv (高等学校化学学报) , 1997, 18 (7) : 1107211121
[ 2 ]　N o rthw est Institu te of P lateau B io logy, Ch inese A cadem y of
Science. T ibetan M ed icine G lossary (藏药志) [M ]1 X in ing:
Q inghai Peop le’s Pub lish ing House, 19911
[ 3 ]　Sh i J G, J ia Z J , Yang L 1 D iterpeno ids from E up horbia m i2
cractina [J ]1 Chem J Ch in U n iv (高等学校化学学报) , 1994,
15 (6) : 86128631
[ 4 ]　L al A R , Cam bie R C, Rutledge P S, et a l1 E nt2p im arane
and en t2ab ietane deterpenes from E up horbia f id j iana [J ]1
P hy tochem istry , 1990, 29 (7) : 2239222461
[ 5 ]　Satti N K, SuriO P, D har K L , et a l1 H igh reso lu tion NM R
and X2ray crystallography data of caudicifo lin from E up horbia
·316·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 6 期 2004 年 6 月
acau lis [J ]1 P hy tochem istry , 1986, 25 (6) : 1411214311
[ 6 ]　Bo rgh i D , Baum er L , Ballab io M , et a l1 Structu re elucida2
t ion of helio scop ino lides D and E from E up horbia ca lyp tra ta
cell cu ltu res [J ]1 J N a t P rod , 1991, 54 (6) : 1503215081
[ 7 ]　J ia Z, D ing Y L 1 N ew diterpeno ids from E up horbia
siebold iana [J ]1 P lan ta M ed , 1991, 57, 56925711 [ 8 ]　L al A R , Cam bie R C, Rutledge P S, et a l1 E nt2atisanediterpenes from E up horbia f id j iana [J ]1 P hy tochem istry ,1990, 29 (6) : 1925219351[ 9 ]　A ppendino G, Bello ro E, T ron G C, et a l1 Po lycyclic fromE up horbia characias [J ]1 F itoterap ia , 2000, 71 ( 2 ) : 13421421
两种毛大丁草多糖 Gbp 和 Gcp 的组成研究
佘志刚1, 唐小江2, 郭志勇1, 陈东淼1, 林永成1Ξ
(11 中山大学化学与化学工程学院, 广东 广州　510275; 　21 广东省职业病防治院 毒理科, 广东 广州　510300)
摘　要: 目的　从毛大丁草的根中分离提取多糖, 测定其组成。方法　毛大丁草根的水提物经脱蛋白、脱色、乙醇沉
淀得两种粗多糖, 再经过 Sephadex G275 和 Sephadex G250 凝胶柱色谱纯化得到两种纯多糖 Gbp 和 Gcp , 用高效凝
胶色谱 (H PGPC)测定Gbp 和 Gcp 相对分子质量, 通过完全酸水解后, 进行三甲基硅醚化的 GC2M S 分析, 测定两种
多糖的组成。结果　Gbp 和 Gcp 重均相对分子质量分别为 6165×105 和 7145×104。Gbp 是由木糖、来苏糖、鼠李
糖、核糖、葡萄糖和半乳糖组成, 其比例约为 3∶3∶3∶2∶6∶2; Gcp 主要由果糖组成, 还有少量葡萄糖和木糖, 其
比例为 24∶4∶1。结论　通过凝胶柱色谱分析, 所提取两种多糖 Gbp 和 Gcp 均为单一、纯净的多糖。
关键词: 毛大丁草; 多糖; 三甲基硅醚化反应
中图分类号: R 28411　　　文献标识码: A 　　　文章编号: 0253 2670 (2004) 06 0614 03
Study on com posit ion of two polysacchar ides Gbp and Gcp
from root of Gerbera p iloselloides
SH E Zh i2gang1, TAN G X iao2jiang2, GUO Zh i2yong1, CH EN Dong2m iao 1, L IN Yong2cheng1
(11 Schoo l of Chem isty and Chem ical Engineering, Sun Yat2sen U niversity, Guangzhou 510275, Ch ina; 21 D epartm ent of
Toxico logy, Guangdong P rovincia l Cen ter fo r O ccupational D isease P reven tion and T reatm ent, Guangzhou 510300, Ch ina)
Abstract: Object　To study the compo sit ion of tw o po lysaccharides Gbp and Gcp w h ich w ere iso la ted
and pu rif ied from Gerbera p iloselloid es (L. ) Cass1M ethods　T he po lysaccharides w ere ex tracted w ith ho t
w ater and p recip ita ted by alcoho l1 P ro tein in the p recip ita tes w as removed by Sevag m ethod1 T he p roducts
w ere fu rther pu rif ied w ith co lum n ch rom atography on Sephadex275 and Sephadex2501 T he mo lecu lar
w eigh ts of Gbp and Gcp w ere m easu red by H PGPC1 T heir compo sit ion s w ere studied by u sing GC2M S af2
ter acid hydro lysis and trim ethylsilyla t ion1 Results　T he w eigh t2average mo lecu lar w eigh ts of Gbp and
Gcp are 6165×105 and 7145×104 respect ively (w ith po lyoxyethylene glyco l as a reference) 1 Gbp is con sist2
ed of lyxo se, xylo se, rob ito se, g luco se, and galacto se, the ra te is 3∶3∶3∶2∶6∶21 Gcp is compo sed of
fructo se, g luco se, and xylo se (24∶4∶1) 1 Conclusion　Gbp and Gcp are show n to be homogeneou s by gel
perm eat ion ch rom atograhy1
Key words: Gerbera p iloselloid es (L 1) Cass1; po lysaccharide; t rim ethylsilyla t ion
　　多糖是一类重要的生命大分子物质, 在生物体
内有重要的生物功能和良好的生物活性, 在生命科
学和医药科学中有广泛的应用, 因而多糖成为具有
吸引力的研究领域[1 ]。我们从鲍鱼和海洋微生物的
菌体中分离出多种有生物活性的多糖, 并对其组成、
结构和药理活性进行了研究[2, 3 ]。近来又从中药毛大
丁草的根部分离出两种多糖 Gbp 和 Gcp , 药理实验
显示这两种多糖是良好的免疫调节作用。毛大丁草
·416· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 6 期 2004 年 6 月
Ξ 收稿日期: 2003210219
基金项目: 广东省中医药局科研资助项目 (101028)3 通讯作者　E2m ail: ceslyc@zsu1edu1cn